Polymerization products of diolefines



Patented May 31, 1932 UNITED STATES PATENT OFFICE 'ILABTIN LUTHER, F MANNHEIM, AND CLAUS HEUCK, OF LUDWIGSHAFIiN-ON-THE- BHINESGERMANY, .A SSIGNOBS TO I. G. FABBENINDUSTRIE AK'I'IENGEBELLSOHAFT, OI FRANK'FORT-ON-THE-MAIN, GERMANY, A CORPORATION OF GERMANY POLYMERIZATION PRODUCTS OI DIOLEFmES Ho Drawing. Application filed May 18, 1929, Serial No. 864,815, and in Germany July if, 1928.

This invention relates to improvements in the manufacture and production of plastic gr elastic polymerization products of diolenes.

We have found that improved plastic and Q elastic polymerization products, which, when vulcanized, yield vulcanizates resembling the products obtained by the vulcanization of crude rubber, are obtained when agents having a reducing action are allowed to act on emulsions of the polymerization products obtained from diolefines such as butadiene, isoprene or dimethylbutadiene, or agents having a reducing or otherwise decomposing ac tion on oxidizing agents, in particular hydrogen peroxide, in case such oxidizing agents have been employed as polymerizers. Sodium bisulphite, sodium hydrosulphite, formaldehyde sodium sulphoxylate, stannous chloride, hydroxylamine or hydrazine or salts thereof, or hydrogen in the presence of catalysts are all suitable, amon others, as reducing agents for the purpose 0 the present invention, and phenols, naphthols, sols of metals or metal oxides, peroxidases and amines, such as I aniline, may be mentioned as examples of agents facilitating the decomposition of oxidizing agents. T e mechanical treatment referred to may, for example, be a treatment of the polymerized product on friction rollers.

By the treatment in accordance with the present invention although the polymerization products themselves are not attacked, they are usually bleached to a marked extent, and are obtained with pale yellow to white colorations. With polymerization products which have been prepared with the aid 0 agents supplying oxygen, such .as peroxides and the like, another valuable action occurs besides the bleaching action, since the agents supplying oxygen which are still present in the product are destroyed, and thus an extensive stabilization ofthe product is effected.-

In particular, the action of the hydrogen peroxide, or other oxidizing agents, which agents are frequently employed in the polymerization, and small quantities of which always remain in the final product, is immediately counteracted by the action of the reof the polymerization pro uct. The amount can easily be controlled, since no'consider able excess of the reducing agent should final l? be present. The agents facilitating the ecomposition of oxidizing agents may even be employed in very small amounts indeed.

The following example will further illustrate how the invention may be carried out in practice but the invention is not restricted thereto. The parts are by volume.

Ewample 1 8 parts of-olein are dissolved in 200 parts of isoprene, and the solution is emulsified by shaking in 350 parts of an 0.5 per cent aqueous solution of ammonia to which 0.5 per cent of glue is added as a protective colloid. The

hydrogen-ion concentration of the emulsion amounts to 8.9. It is a stable emulsion, and" by adding 5 parts of 30 per cent hydrogen peroxideand heating for two days at 50 C. a product, containing the polymerization product in dispersion in the manner that rubber is contained in latex, is obtained. 30 parts of a 10 per cent aqueous sodium hydrosulphite solution are then added to the product. The hydrogen peroxide still present is thus destroyed and by precipitation in the usual manner a white polymerization product is obtained which has good properties, in par-' ticular good stability.

By employing 50 parts of an 0.5 per cent solution of phenol or aniline in water instead of the sodium hydrosulphite solution, a stable polymerization product is. similarly obtained, which, however, is somewhat darker in color. 7

What we claim is:- 1. In the production of plastic or elastic products from dproducts obtainedby the polymerization of olefines in the api'esence of hydrogen peroxide, the step of owing a su stance efl'ecting decomposition of hydrogen peroxide to act on an emulsion of the said 10 products.

2. In the production of plastic or elastic roducts from polymerizatlon products of diolefines, the step of allowing to act on an emulsion of the said products u to about 5 per cent, by weight of the g2 ymerization product, of sodium hydro-sulp to solution.

3. In the production of plastic or elastic products from roducts obtamed by the poly- -merization of 'olefines in the resence of an oxidizing agent, the step of a owing to act on an emulsion of the said products up to I about 5 per cent, by weight of the olymerization product, of sodium hydrosu phite solution.

4. In the production of plastic or elastic products from products obtained by the polymerization of butadiene in the presence of hydrogen peroxide, the step of allowing to act on an emulsion of the said products up to about 5 per cent, by weight of the polymerizationproduct, of sodium hydrosulphite solution.

5. In the production of plastic or elastic Y products from products obtained by the poly- Q merization of diolefines in the presence of hydrogen peroxide, the step of allowing sodiwn hydrosulphite to act an an emulsion of the said products.

p 6. In the production of plastic or elastic 40 products from jproducts obtained by the pol merization o diolefines in the presence of 'hy rogen eroxide, the step of allowing sodium bisulp ite to act on an emulsion of the said products.

7. In the production of plastic or elastic products from products obtained by the polymerization of diolefines in the presence of hydrogen peroxide, the step of allowing stannous chloride to act on an emulsion of the said products.

. In testimony whereof we havehereun set our hands.

MARTIN LUTHER.

w CLAUS HEUCK. 

